Aqueous dispersion of aminoplast and butene-2-diol-1, 4



United States Patent 3,135,710 BlSEEREiION 0F AMINGPLAST ANDBUTENE-Z-DIGL-lfl Peter L. de Benneville, Philadelphia, Pa, assignor toRobin dz Haas Company, Philadelphia, Pa, :1 corporaof Delaware NoDrawing. Filed Sept. 22, 1950, Ser. No. 57,636 8 Claims. (Cl. 26tl29.4)

" "derivatives, such as N,N'-ethyleneurea and methylol melamines andureas and their alkylated derivatives and also N,N-trimethyleneurea,have been applied to Wool and cellulosic fabrics, such as cotton, forthe purpose of imparting crush-resistance and reduced shrinkage onlaundering. However, fabrics treated with these condensates pick upchlorine during bleaching operations using chlorine, such as those usingit in the form of a hypochlorite. On ironing the fabrics that have beenbleached in this manner, severe discoloration and/or loss in tensileand/or tear strengths have generally resulted. in those cases wheresevere discoloration is encountered, the treatment with thesecondensates is unsuitable, especially when a White fabric is desired. Insome cases, as much as 90% loss in strength is encountered as a resultof the action of heat, as in ironing, on fabrics treated with thesecondensates and bleached with chlorine. The presence on a fabric of athermoset condensate of formaldehyde with melamine frequently gives riseto some discoloration of the fabric on the mere treatment with ahypochlorite bleach unless care is taken to avoid excess chlorine andelevated temperatures. Ironing in such cases serves to aggravate thediscoloration.

U.S. Patent 2,794,754 discloses the use of a mixture of an aminoplastcondensate with a compound containing a plurality of vie-epoxy groups.The compounds of this patent, however, are comparatively inefficient inprotecting the fabric from chlorine damage by certain nitrogencontaining condensates, and especially those of formaldehyde withN,N-ethyleneurea and melamine, when used in admixture therewith. Inaddition, the vie-epoxy compounds tend to pick up iron in hard Water andthereby produce a discoloration on washing of the fabric which cannot beremoved by normal bleaching operations.

It has been found in accordance with the invention that theincorporation of a minor proportion of butene-Z-diol- 1,4 in aqueoussolutions of water-soluble aminoplast condensates selected from thegroup consisting of condensates of formaldehyde with aminotriazines,certain triazones, N,N'-trimethyleneurea, and N,N-ethyleneurea, andtheir alkylated derivatives serves to eliminate, or reduce to withinpractical limits, the chlorine damage that would otherwise occur as aresult of the treatment with such aminoplasts. Surprisingly, theimprovement is accomplished without the necessity to apply excessivequantities of the shrink-proofing or crease-proofing composition inspite of the fact that the diol is incapable of creaseproofingcellulosic fabrics when applied without an aminoplast under conditionssimilar to those under which. the mixture is applied. The diol of thepresent invention is from five to ten times as efficient as theVic-epoxy compounds of the U.S. Patent 2,794,754 in reducing chlorinedamage by discoloration and degradation caused by the "ice aminoplastcondensates and have little or no tendency to pick up iron from hardwaters as the Vic-epoxy compounds do.

The aminoplast constitutes the major or predominant part of theshrink-proofing, crease-proofing, or crushproofing components of thecomposition. The diol component constitutes from about 5% to about 40%by weight of the effective components, that is the total weight of theaminoplast and diol. For most purposes, from the standpoint of cost,efficiency, optimum freedom from discoloration, and minimum tensile losson ironing or heating after chlorination, it is preferred to use from 5%to 20% by weight of diol and 95 to by weight respectively of aminoplast.

in accordance with the present invention, the aminoplast compositionswith which the invention is concerned are water-soluble in character andinclude the simple condensates of N,N-ethyleneurea, certain triazonesdescribed hereinafter and aminotriazines, such as melamine or itsderivatives including N-(C -C )alkylmelamines, N,N-di-(Cf-CQalkylmelamines, and N,N'-di-(C C )alkylmelamines, withformaldehyde as well as the alkylated methylol derivatives thereof, inwhich the alkylation is effected with lower alcohols from 1 to 3 carbonsor with small proportions of higher alcohols, such as the butyl alcoholsor with mixtures of such higher alcohols with the lower alcohols, sothat in any event the alkylated methylol derivatives are water-solubleor self-dispersible readily in water. Any Water-soluble condensate offormaldehyde with melamine, N,N-ethyleneurea, or N,N'-tri.rnethyleneureamay be employed. Examples of specific compounds that may be used includetn'methylolmelamine, dimethylol-N,N'-ethyleneurea, anddimethylol-N,N-trimethyleneurea. The triazones that may be used includethe polymethylol tetrahydro-s-triazones substituted in the 5- positionby an alkyl or hydroxyalkyl group. These triazones have the Formula I:

, I i 1) where R is selected from the group consisting of2-hydroxyethyl, 2-hydroxypropyl, and alkyl groups having 1 to 4 carbonatoms. In addition, the alkylated derivatives of these polymethylolcondensates obtained from the lower alcohols from methyl through butylmaybe employed. Examples include dimethoxymethyl-N,N-dimethylmelamine,dimethoxymethyl N,N ethyleneurea,

dimethoxymethyl '5 ([3 hydroxymethyl)tetrahydro-striazone-Z, and so on.Again, it should be noted that the condensates employed as component Amay be fairly sharply defined compounds including those just named asWell as others, or it may comprise mixtures of compounds of varyingdegrees of substitution wherein the number of methylol groups oralkoxymethyl groups may be different in the several compounds within themixture. For the most efficient action, the aminoplasts derived fromN,N'- ethyleneurea and from melamine are preferred.

The aqueous solution of the water-dispersible compouents, including theaminoplast and the diol, may contain each of such components in aconcentration in about 2 to 25% or more by weight. The particularconcentration applied in any given instance may depend on thepurpose'for which the mixture is applied and on the particular substrateor fabricto which it is applied; In case of cotton, the concentration ispreferably from 2 to 12%, whereas in application to rayon theconcentration I is preferably 5 to 20%, when the purpose of theapplication is to impart crease-resistance, crush-resistance, orshrinkage stabilization. In the case of WOOl, the concentration ispreferably from to 15%. While it is gen-' erally unnecessary, theaminoplast condensate and the diol may be reacted together provided anysuch reaction leaves'the final condensate in'a water-soluble Condition.However, for most purposes, it is preferred not to coreact thesecomponents. The solution containing the mixture of the aminoplast anddiol components or the co-reac'ted components is stable when subjectedto ordinary conditions of storage and can be soldfshipped and stored assuch. Shortly be fore use, an acidic catalyst may beadded, if desired,as pointed out hereinafter.

' "An acidic catalyst for catalyzing the condensation of the ,aminoplastand the reaction of the cellulose with the diol and the aminoplast isapplied'to the fabric either simultaneously with the aminoplastcondensate and diol or before'or after the'mixture thereof is applied.Prefe'r ably, the'acidic catalyst is dissolved in the aoueous solutionof the mixture of aminoplast condensate and diol. Suitable catalystsinclude phosphate, ammonium fluoborate, ammonium thiocyanate,hydrochloric or other acid salts of a hydroxy aliphatic amine including2- methyl -2 amino l 'propanol, 2 methyl- 2 amino- 1,3 propandiol, tris-(hydroxymethyl) aminomethane, 2 phenyla 2 .amino 1 propanol, 2- methyl 1J methylamino 1 pentanol, 2 aminobutainol, triethanolamine,Z-amiho-Z-ethyl-l-butanol, and. also ammonium chloride,v pyridinehydrochloride, aluminum chloride,

benzyldimethylammonium oxalate, magnesium perchlorate, zincsilico-fluoride, zinc perchlorate, magnesium thio cyanate, zincvthiocyanate; Zinc iiuoborate, zinc nitrate, boron fluoride, andespecially the boron fluoride ether complex of the boron fluoride watercomplex, hydrogen fluoride, hydrochloric acid, ammonium chloride, amnoacid'fluoride, phosphoric aci.., 'oxalicacid, tartaric acid, citricacid, sulfuric acid, and sodium bisulfate. The preferred catalystswhichseem to be outstanding in their eihciency ofaction and freedom fromdetrimentaleffect 1 on fabrics, especially with cellulosic types offabrics, are the zinc salts such asv zinc fiuoborate and zinc nitrate.

The catalyst is generally introduced, into the aqueous solution of thecondensates at a concentration of about 0.1 to 2% and preferablyapproximately 1%. The catalyst may be presentin an amount from about /2to about on the total weight of aminoplast condensate and diol.

The compositions of the present invention may be ap- 7 plied to fibersfilaments, yarns, or fabrics of wool or cellulosic type and especiallythose of cotton or rayon for various purposes. For example, they maybeapplied 7 simply; to modify thefeel or texture of the surtaceofthe-fabrics. When applied in greater quantities, the composition of thepresent inventionmay be used to make the .fabrics wrinkle-resistant,crush-resistant and crease-resistant; composition: serves to provideproportionately increased reduction in shrinkage of the treated fabricon launderingyand when =about3 to 7% by weight ofthe composition, based'onithe weightof the fabric, is applied, the

The application of increasing amounts'of the Wool or'cellulosic fabricisigenerally substantially stabilized a'g'ainstgshrinkage on laundering.The application of the composition of the present invention may beemployedifor .the purpose of-aiding embossing operations. It also may beapplied to fabrics as'part. ofa process for theirconversion' to plissefabrics andembossed fabrics.

. The aqueous solution of the aminoplast condensate and diol may beapplied. by spraying, brushingpdipping, as in f paddinggor'byroller-coating; Afterjtheapplication, ex-

' icess may bel-removed, as by squeezing or squeegeeingi t The treatedfabric is then dried, such 'as by rairdryingi-at room temperature or bythe treatment with heated ain under conventional conditions 1 Afterthefabric has been dried-,; the composition is baked or cured on the fabricat a temperature of about 220 to 450 F. or higher, depending on theparticular substrate. The time may be varied generally in inverseproportions to the temperature. For example, the time may vary fromabout five seconds to half an hour. A

time of 30 seconds at 400 Pris quite practical and a time of 15 to 30minutes'at 220 F. is generally satisfactory. The baking operation maysimply be a continuation of the drying operation so that drying andcuring may be efiected in essentially a one-stage procedure.

The drying and/orthe baking may be eifected by any suitable means forapplying the heat, such as by'the application of heated air currents, byinfra-red radiation or by high frequency electric induction.

in the following examples, which are illustrative of the invention, theparts and percentages are given by weight unless otherwise noted;'Ihechlorination test method referred to in the examples follows theA.A.T.C.C. (69-.

1952) procedure in general except the temperature of chlorination andthat of ironing indicated hereinafter. The actual procedure usedinvolves the treatment with. a

hypochlorite solution containing 0.25% available chlorine at atemperature of 140 F.i2 F. for 15 minutes with intermittent stirring.This treatment is followed by rinses in'six freshwater baths at 70to P.with a'squeeze between rinses and drying in air atroom temperature.

The drying is'followed by conditioning for at least four hours at 70Rand 65% relative humidity; The sample is 'iroued'at 400'F. (irontemperature) for 30 seconds.

The chlorine'damage referred to hereinbelow is the percentage loss intensile strength referred to hereinbelow I andfis calculated by the.formula is... V, 7

t is the tensile strength after chlorination only, -and where t thetensile strength after both chlorination and ironing (or scorch test). HV

ExAivirLE t 7 r (a) An aqueous solution is prepared containing 1% ofbutene-2 diol-L4, 5% of dimethylol-N,N-ethyleneurea, and 0.4% of Zincnitrate as a catalystf A white cotton fabric is padded through thissolution, dried at 220 F for 5 minutes, and'then 'heatied at 320 F."for3.minutes to f cure the resin.

" :(bi) Another piece ofthe same cotton fabric is treated in the sameway except that the diol was reduced to'0.5%.

'(c) 'Another-pieceof the same cotton fabricis treated '7 in the sameway except that the diol was'reduced to. 0.25% Q '(d) Another piece ofthe same cotton fabric-is treated in the 'sam e way exceptthat thediolwas reduced to zero. After-five full Sanforize washes, thefabricsaresub- '-3'ected to the chlorinationtest above. In all'cases, yellowingafter ironing is either non-existent or negligible. The resultsof-testingxfor, crease-proofing and chlorine damageare shown in thefollowing'table (wherein the values given for: crease-re'co "S'nilarresults are also obtainedwhen the urea de-. rivative is replaced withdimetlioxymethyl-l LNkthylenevery are theaverage of the EXAMPLE 2 Anaqueous solution is prepared containing 1.0% butene-2-diol-l,4, 5% ofdimethylol-N,N'-trirnethyleneurea, and 0.5% of zinc fiuoborate as acatalyst. A white cotton fabric is padded through this solution, driedat 240 F. for 5 minutes, and then heated at 340 F. for 5 minutes to curethe resin.

After five full Sanforize washes, the fabric is subjected to thechlorination test with negligible discoloration.

EXAMPLE 3 (a) An aqueous solution is prepared containing 0.5% ofbutene-2-diol-1,4, 5% of dimethylol trimethoxymethyl melamine, and 0.5%of zinc fluoborate as a catalyst. Application to white cotton fabric ismade by the procedure of Example 1.

(b) Another piece of the same cotton fabric is treated in the same wayexcept the diol is omitted. After five full Sanforize washes andsubjection to the chlorination test EXAMPLE 4 (a) An aqueous solution isprepared containing 1% of butene-2-diol-1,4, 6% ofdimethylol-S-ethyl-tetrahydrotriazone-Z, and 1.0% of zinc nitrate as acatalyst. Application to white cotton fabric is made by the procedure ofExample 1.

(b) Another piece of the same cotton fabric is treated in the same wayexcept the diol is omitted, After five full Sanforize washes andsubjection to the chlorination test, the results are as listed in Table111:

Table III Chlorine Damage Diseoloration on Chlorination and IroningPercent Loss in Tensile Strength Example Slight. Yellow.

(c) Similar results are obtained when the triazone is replaced withdimethylol-S-(fi-hydroxyethyl)-tetrahydIo-striazone-Z.

I claim:

1. A composition comprising an aqueous dispersion of a mixture of to byweight of a water-dispersible aniinoplast condensate selected from thegroup consisting of condensates of formaldehyde with a compound selectedfrom the group consisting of N,N-ethyleneurea, N,N-trimefliyleneiuea, atetrahydro-s-triazone-Z substituted in the 5-position with a groupselected from the group consisting of 13-hydroxyethyl, ,B-hydroxypropyl,and (C -C -alltyl groups, and a melamine and 5 to 40% by weight ofbutene-2-diol-1,4.

2. A composition comprising an aqueous dispersion of a mixture of 60 to95% by weight of a water-dispersible aminoplast condensate offormaldehyde with N,N'-ethyleneurea and 5 to 40% by weight ofbutene-2-diol-1,4.

3. A composition as defined in claim 2 in which the aminoplast is awater-disnersible dimethylol-N,N'-ethyleneurea.

4. A composition as defined in claim 2 in which the aminoplast is adimethoxymethyl-N,N'-ethyleneurea.

5. A composition comprising an aqueous dispersion of a mixture of 60 to95% by weight of a water-dispersible aminoplast condensate offormaldehyde with melamine and 5 to 40% by weight of butene-2-diol-1,4.

6. A composition as defined in claim 5 in which the aminoplast is awater-dispersible methylated polyrnethylolelarnine.

7. A composition as defined in claim 5 in which the aminoplast is adimethylol trimethoxymethylmelarnine.

8. A composition as defined in claim 5 in which the aminoplast is adimethylol-5-ethyl-tetrahydro-s-triazone-Z.

References Cited in the file of this patent UNITED STATES PATENTS2,596,268 Meiier May 13, 1952 2,640,041 Bruner et al. May 26, 19532,794,754 Schroeder June 4, 1957 2,890,242 Kress June 9, 1959 2,950,553Hurwitz Aug. 30, 1960 2,965,436 Domenico et al. Dec. 20, 1960 2,966,473Biefeld et a1 Dec. 27, 1960 3,005,792 Craig et al. Oct. 24, 1961

1. A COMPOSITION COMPRISING AN AQUEOUS DISPERSION OF A MIXTURE OF 60 TO95% BY WEIGHT OF A WATER-DISPERSIBLE AMINOPLAST CONDENSATE SELECTED FROMTHEGROUP CONSISTING OF CONDENSATES OF FORMALDEHYDE WITH A COMPOUNDSELECTED FROM THE GROUP CONSISTING OF N,N''-ETHYLENEUREA,N,N''-TRIMETHYLENEUREA, A TETRAHYDRO-S-TRIAZONE-2 SUBSTITUTED IN THE5-POSITION WITH A GROUP SELECTED FROM THE GROUP CONSISTING OFB-HYDROXYETHYL, N-HYDROXYPROPYL, AND (C1-C4)-ALKYL GROUPS, AND AMELAMINE AND 5 TO 40% BY WEIGHT OF BUTENE-2-DIOL-1,4.